EP1178956A1

EP1178956A1 - Substituted n-cyano amidines

Info

Publication number: EP1178956A1
Application number: EP00929495A
Authority: EP
Inventors: Ernst Rudolf F. Gesing; Achim Hense; Kristian Kather; Stefan Lehr; Hans-Jochem Riebel; Lothar Rohe; Katharina Voigt; Mark Wilhelm Drewes; Dieter Feucht; Rolf Pontzen; Ingo Cond. Estancia Marambaia WETCHOLOWSKY
Original assignee: Bayer AG
Current assignee: Bayer CropScience AG
Priority date: 1999-05-12
Filing date: 2000-05-04
Publication date: 2002-02-13
Also published as: MXPA01011452A; HK1044530A1; DE19921886A1; AU765922B2; PL351671A1; KR20020005008A; BR0010447A; CA2373429A1; AU4755300A; CN1350517A; WO2000069813A1; JP2002544255A

Abstract

The invention relates to novel substituted N-cyano amidines of general formula (I) in which: R1 represents hydrogen or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl or alkyl aryl, and; R2 represents benzo-anellated, pyrido-anellated or thieno-anellated cycloalk(en)yl, oxacycloalk(en)yl or thiacycloalk(en)yl, whereby all cyclic and heterocyclic groupings can be substituted. The invention also relates to a method for producing the substituted N-cyano amidines and to their use as herbicides.

Description

Substituted N-cvano-amidines

The invention relates to new substituted N-cyano-amidines, a process for their preparation and their use as herbicides.

It is already known that certain substituted N-cyano-guanidines have herbicidal properties (cf. DE-A-2505301, US-A-4661520, US-A-4684398, US-A-4689348, J. Agric. Food Chem. 37: 809-814 (1989)). The properties of the previously known substituted N-cyano-guanidines, however, do not meet the high requirements of modern plant treatment agents in various aspects.

The new substituted N-cyanoamidines of the general formula (I)

in which

R ^{1 stands} for hydrogen or for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl and

R ² for each benzo-fused, pyrido-fused or thieno-fused

Cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalk (en) yl, where all cyclic and heterocyclic groups can be substituted,

found.

The general formula (I) includes the possible E and Z configuration isomers. In the definitions, the hydrocarbon chains, such as alkyl, alkenyl or alkynyl, are each straight-chain or branched.

Preferred substituents of the radicals listed in the formulas mentioned above and below are explained below.

R ¹ preferably represents hydrogen, optionally substituted by cyano, halogen, dC ₄ -alkoxy, C 1 -C ₄ -alkylthio, Q-alkylsulfinyl or C 1 -C ₄ -alkylsulfonyl-substituted alkyl having 1 to 6 carbon atoms, for each counter- appropriate, halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, represents in each case optionally cyano-, halogen or Cι-C ₄ - substituted alkyl cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl moiety, in each case optionally substituted by nitro, cyano, halo, Cι-C ₄ - alkyl, _{Cι-C4-haloalkyl,} Cι-C ₄ alkoxy or C

C ₄ haloalkoxy-substituted aryl or arylalkyl, each having 6 or 10 carbon atoms in the aryl groups and optionally 1 to 4 carbon atoms in the alkyl part.

R preferably stands for benzo-fused, pyrido-fused or thieno-fused cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalk (en) yl from the list below

where all cyclic and heterocyclic groups can preferably be substituted by one of the groups listed below:

Nitro, hydroxy, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, halogen, CC ₄ -alkyl, -C-C -haloalkyl, Cι-C ₄ -alkoxy, Cι-C -haloalkoxy, Cι-C ₄ -alkylthio, C ] -C ₄ -haloalkylthio, -C-C ₄ -alkylsulfinyl, Q- C ₄ -haloalkylsulfonyl, -C-C ₄ -alkylsulfonyl, -C-C ₄ -haloalkylsulfonyl,

Cι-C alkylamino, di- _(Cι-C4 alkyl) amino, Cι-C alkyl-carbonyl, Cj-C ₄ - alkoxy-carbonyl, C i -C ₄ - alkylamino-carbonyl, di- (C i -C ₄ alkyl) amino carbonyl, _Cι-C4 alkyl-carbonyl-amino, Cι-C ₄ -alkoxy-carbonyl-amino, - C ₄ -alkyl-amino-carbonyl-amino, _Ci-C4 Alkyl sulfonyl amino.

is particularly preferably hydrogen, each optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfmyl, ethylsulfinyl, n- or i-propy - Isulfmyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally substituted by fluorine, chlorine or bromine Ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl , for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl or benzyl.

R> 2 particularly preferably represents one of the cyclic and heterocychic groupings mentioned above, the substituents being selected from one of the groupings listed below:

Nitro, hydroxy, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, Trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethyl, fluorodichloromethoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethyldifluoromethyldifluoromethyl, difluoromethylchlorofluoromethyl Methylsulfmyl, ethylsulfonyl, trifluoromethylsulfmyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, n- or i-butylroyl, ethoxy, methoxy, methoxy or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acetylamino, propionylamino, n- or i-

Butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, n- or i-propylaminocarbonylamino, methylsulfonylamino, ethylsulfonylamino, n- or i-propylsulfonylamino.

R ¹ very particularly preferably represents hydrogen and in each case methyl, ethyl, n- or i substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfmyl, methylsulfonyl, ethylsulfonyl -Propyl. R very particularly preferably represents benzo-fused cycloalk (en) yl from the list below

where all cyclic groups can be substituted by one of the groups listed above:

R ¹ most preferably represents hydrogen, methyl, ethyl or n- or i-propyl.

R ² most preferably represents one of the following groups:

According to the invention, preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as preferred.

According to the invention, particular preference is given to the compounds of the formula (I) in which a combination of those listed as particularly preferred above

Meanings exist. According to the invention, very particular preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred.

Most preferred according to the invention are the compounds of formula (I) in which there is a combination of the meanings listed as most preferred above.

The general definitions of radicals listed above or those specified in preferred ranges apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.

The new substituted N-cyanoamidines of the general formula (I) have interesting biological properties. They are particularly characterized by their strong herbicidal activity.

The new substituted N-cyano-amidines of the general formula (I) are obtained if N-cyano-imidic acid esters of the general formula (II)

in which

R has the meanings given above and

R 'represents alkyl,

with amino compounds of the general formula (III) I _ N _N (III)

H ^' Η in which

R has the meanings given above,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.

If, for example, ethyl N-cyano-propanimidate and indan-2-yl-amine are used as starting materials, the course of the reaction in the process according to the invention can be outlined using the following formula:

Formula (II) provides a general definition of the N-cyanoimidic acid esters to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I). In the general formula (II), R ¹ preferably has the meaning which has already been given above as preferred, particularly preferred, very particularly preferred or most preferred for R ¹ in connection with the description of the compounds of the general formula (I) according to the invention has been; R 'preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl. The N-cyano-imidic acid esters of the general formula (II) are known and / or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 104 (1982), 235-239; loc. Cit. 106 (1984), 2805-2811; J. Org. Chem. 28 (1963), 1816-1821; loc. Cit. 46 (1981), 1457-1465; Synthesis 1983, 402-404; Tetrahedron Lett. 21 (1980) , 909-912).

Formula (III) provides a general definition of the amino compounds to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I). In the general formula (III), R ² preferably has the meaning which has already been given above in connection with the description of the compounds of the general formula (I) according to the invention as preferred, particularly preferred, very particularly preferred or most preferred for R ² .

The amino compounds of the general formula (III) are known and / or can be prepared by processes known per se (cf. J. Am. Chem. Soc. 88 (1966), 2233-2240; loc. Cit. 95 (1973), 4083-4084); J. Chem. Soc. C 1966, 717-722; Synthesis 1980, 695-697; Tetrahedron 24: 3681-3696 (1968); loc. cit. 50 (1994), 3627-3638).

The process according to the invention for the preparation of compounds of the general formula (I) is optionally carried out using a reaction auxiliary. The usual inorganic or organic bases or acid acceptors are generally suitable as reaction aids for the process according to the invention. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, hydrogen carbonates, hydrides, hydroxides or alkanolates, such as, for example, sodium, potassium or calcium acetate, lithium, sodium, potassium or Calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, Sodium or potassium methoxide, ethanolate, n or i propanolate, n, i, s or t butanolate; also basic organic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl- benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5-

Ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo [4,3, 0] -non-5-ene (DBN), or 1,8-diazabicyclo [5, 4.0] -undec-7-ene (DBU).

In most cases, one of the above reaction aids can be dispensed with.

The process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a diluent. In addition to water, the main diluents are inert organic ones

Solvent. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol,

Ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be carried out when carrying out the process according to the invention

Process can be varied over a wide range. Generally you work at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

The process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.

To carry out the process according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent, if appropriate in the presence of a reaction auxiliary, and the reaction mixture is generally stirred at the required temperature for several hours. Working up is carried out according to customary methods (cf. the production examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used. The active compounds according to the invention can e.g. can be used in the following plants:

Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium,

Ranunculus, Taraxacum. Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasumirumum, Scalumumum, Scalumumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera, Aegilops, Phalaris.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means limited to these

Limited genera, but extends in the same way to other plants.

Depending on the concentration, the active compounds according to the invention are suitable for combating total weeds, e.g. on industrial and track systems and on

Because of and places with and without tree cover. The active compounds according to the invention for weed control in permanent crops, e.g. Forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture areas as well for selective weed control in annual crops.

The compounds of formula (I) according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for selective use Control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both pre- and post-emergence.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Possible solid carriers are: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite,

Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight

Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.

Known herbicides are suitable for the mixtures, for example

Acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin,

Azimsulfuron, benazolin (-ethyl), benfüresate, bensulfuron (-methyl), bentazone, Benzobicyclone, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac (- sodium), Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butroxydim, Butylate, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chloro-methoxyfen Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlor- sulfuron, Chlortoluron, Cinidon (-ethyl), Cinmethylin, Cinosulfuron, Clefoxydim,

Clethodim, Clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyra-sulfüron (-methyl), Cloransulam (-methyl), Cumyluron, Cyanazine, Cybutryne, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl) D, 2,4-DB, 2,4-DP, Desmedipham, Diallate, Dicamba, Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dimefüron, Dimepiperate, Dimethachlor,

Dimethametryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Diethiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Ethoxysulfuron, Fenoxapan- ethyl), fentrazamide, flamprop (-isopropyl), flamprop (-isopropyl-L), flamprop (- methyl), flazasulfuron, florasulam, fluazifop (-P-butyl), fluazolate, flucarbazone,

Flufenacet, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumet-sulam, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Fluprop-acil, Flurpyrsulfuron (-methyl, -sodium), Flurenol (-flurene), , Fluroxypyr (- methyl), Fluφrimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide, Fomesafen, Glufosinate (-ammonium), Glyphosate (-isopropylammonium), Halosafen, Haloxyfop-

(-ethoxyethyl), Haloxyfop (-P-methyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Iodosulfuron (-methyl, -sodium), Ioxynil, Isalin Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, MCPP, Mefenacet, Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuronamox, Moxauron, Moxa Metsulfuron (-methyl), Molinate, Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paraquat, Methalonex, Pendargon Phenmedipham, Piperophos, Pretilachlor, Primisulfuron (-methyl), Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propyzamides, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazolates, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyridates, pyriminobac (- methyl), pyrithiobac (-sodium), quinchlorac, quinmeropac, quinoclamopac (-P-ethyl), Quizalofop (-P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulfuron,

Tebutam, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thiafluamamide, Thiazopyr, Thidiazimin, Thifensulfuron (-methyl), Thiobencarb, Tiocarb-azil, Tralkoxydim, Triallate, Triasulfüron, Tribenuroni-, Tribenuron (-di- Trifluralin and triflusulfuron.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.

The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.

The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the examples below. Manufacturing examples;

example 1

A mixture of 0.98 g (10 mmol) of N-cyanoethanimidic acid methyl ester, 1.42 g (10 mmol) of 1, 2,3,4-tetrahydro-1-naphthylamine and 20 ml of water is stirred for 12 hours at room temperature ( about 20 ° C) stirred. The crystalline product is then isolated by suction, washed with a little water and diethyl ether and dried on a clay disk.

1.3 g (62% of theory) of N 'cyano-N- (1,2,3,4-tetrahydro-1-naphthyl) ethanimidamide with a melting point of 113 ° C. are obtained.

Analogously to Example 1 and in accordance with the general description of the production process according to the invention, it is also possible, for example, to prepare the compounds of the general formula (I) listed in Table 1 below.

Table 1: Examples of the compounds of the formula (I)

Application examples;

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the active ingredient preparation in such a way that the desired amount of active ingredient is applied per unit area. The concentration of the spray liquor is chosen so that the desired amount of active ingredient is applied in 1000 liters of water per hectare.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:

0% - no effect (like untreated control) 100% = total destruction

In this test, for example, the compound according to Preparation Example 1 shows a strong action against weeds. Example B

Post emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

Test plants with a height of 5 - 15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that in

1000 1 water / ha the desired amounts of active ingredient are applied.

It means:

0% = no effect (like untreated control)

100% = total annihilation

In this test, for example, the compound according to Preparation Example 1 shows a strong action against weeds.

Claims

claims

1. Substituted N-cyanoamidines of the general formula (I),

in which

R ^{2 represents} in each case benzo-fused, pyrido-fused or thieno-fused cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalk (en) yl, it being possible for all cyclic and heterocyclic groups to be substituted.

2. Compounds according to claim 1, characterized in that

R ¹ for hydrogen, optionally substituted by cyano, halogen, -CC ₄ -alkoxy, CC ₄ -alkylthio, -C-C ₄ -alkylsulfinyl or -C-C ₄ alkylsulfonyl-substituted alkyl having 1 to 6 carbon atoms, each optionally halogen-substituted alkenyl or alkynyl, each having 2 to 6 carbon atoms, for cycloalkyl or cycloalkylalkyl, each optionally substituted by cyano, halogen or C 1 -C ₄ -alkyl, each having 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl part , or for each optionally by nitro, cyano, halogen, C 1 -C ₄ -alkyl, C 1 -C ₄ haloalkyl, dC ₄ alkoxy or Ci- C ₄ -haloalkoxy-substituted aryl or arylalkyl each having 6 or 10 carbon atoms in the aryl groups and optionally 1 to 4 carbon atoms in the alkyl part, and

R represents in each case benzo-fused, pyπdoannellierter or thieno-fused cycloalk (en) yl, oxacycloalk (en) yl or thiacycloalk (en) yl from the list below,

all cyclic and heterocychic groups preferred

15 may be substituted by one of the groupings listed below:

Nitro, hydroxy, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, halogen, C 1 -C 4 alkyl, C 1 -C ₄ haloalkyl, C 1 -C alkoxy,

20 Cι-C -haloalkoxy, Cι-C ₄ alkylthio, C _t -C ₄ haloalkylthio, Ci- C ₄ alkylsulfinyl, _{Cι-C4-haloalkylsulfinyl,} _{Cι-C4-alkylsulfonyl,} _{Cι-C4-haloalkylsulfonyl,} Cι-C ₄ alkylamino, di- (dC ₄ alkyl) - amino, Cι-C alkyl-carbonyl, Cι-C ₄ -alkoxy-carbonyl, C i -C - alkyl - amino -carbonyl, di- (C] -C ₄ -alkyl) -amino-carbonyl, Cι-C ₄ -alkyl carbonyl-amino, C ι -C ₄ - alkoxy-carbonyl-amino, C ι -C ₄ - alkyl- amino-carbonyl-amino, -C-C ₄ alkyl sulfonyl-amino.

3. Compounds according to claim 1 or 2, characterized in that

R ¹ for hydrogen, for each optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfmyl, ethylsulfinyl, n- or i-propyl- sulfmyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, for each optionally substituted by fluorine, chlorine or bromine, ethenyl, propenyl , Butenyl, ethynyl, propynyl or butynyl, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, or for each optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i- Propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl or benzyl, and

R ^{2 represents} one of the cyclic and heterocyclic groups mentioned in claim 1 or 2, where the substituents can be selected from one of the groups listed below: nitro, hydroxyl, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, fluorine, chlorine, bromine, Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluorodichloromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, trifluoromethylthio, methylifylsulfonyl, methylsulfylsulfylmethylsulfylmethylsulfylmethylsulfylmethylsulfylmethylsulfonyl, methylsulfonylmethylsulfonyl, methylsulfylmethylsulfonyl, methylsulfonyl, methylsulfylsulfyl, methylsulfylsulfyl, methylsulfonyl, methylsulfylsulfyl, methylsulfonyl, methylsulfyl, methylsulfonyl, methylsulfylsulfyl, methylsulfyl, methylsulfonyl, methylsulfonyl Methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylamino- carbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylaminocarbonylamino, ethylaminocarbonylamino, n- or i-propylamino-carbonylamonylamino, - or i-propylsulfonylamino.

4. Compounds according to any one of claims 1 to 3, characterized in that

R ^{1 stands} for hydrogen and for methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfmyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, and

R stands for benzo-fused cycloalk (en) yl from the list below

where all cyclic groups can be substituted by one of the groups listed below:

Nitro, hydroxy, amino, cyano, carbamoyl, thiocarbamoyl, formylamino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, Trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluorodichloromethoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethyllifluoromethyl Fluorodichloromethylthio, methylsulfmyl, ethylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, n-, methoxycarbonyl or i-propoxycarbonyl,

Methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, acetylamino, propionylamino, n- or i-butyroylamino, methoxycarbonylamino, ethoxycarbonylamino, n- or i-propoxycarbonylamino, methylaminocarbonylamino, methylaminocarbonylamino i-

Propylaminocarbonylamino, methylsulfonylamino, ethylsulfonylamino, n- or i-propylsulfonylamino.

5. Compounds according to any one of claims 1 to 4, characterized in that

R ^{1 represents} hydrogen, methyl, ethyl or n- or i-propyl, and

R ^{2 represents} one of the following groupings:

6. A process for the preparation of compounds according to any one of claims 1 to 5, characterized in that N-cyano-imidic acid esters of the general formula (II)

in which

R has the meanings given in one of claims 1 to 5 and

R 'represents alkyl,

with amino compounds of the general formula (III)

R '

. N. (III)

H H in which

R ^{2 has} the meanings given in one of claims 1 to 5, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.

7. Herbicidal agents, characterized by the content of at least one compound according to one of claims 1 to 5 and conventional extenders.

8. Use of at least one compound according to one of claims 1 to 5 for combating undesirable plants.